Vinyl chloride fluorination

Particularly the chlorinated compounds have enjoyed range of applications vinyl chloride (chloro-ethene) as monomer for the production of PVC, tetra- and trichloroethenes as solvents for degreasing, and the insecticides l,l,l-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and isomers of hexachlorocyclohexane (HCH) (benzene hexachloride). The biodegradation of fluorinated aliphatic compounds is generally different from the outlines that have emerged from investigations on their chlorinated, brominated, and even iodinated analogues. They are therefore treated separately in Part 4 of this chapter. 

During hydrogenation of vinylic chlorides, both saturation of the double bond and hydrogenolysis of the C-Cl bond take place.433 35 Also, selective hydrogenolysis of chlorine occurs in the presence of fluorine atoms on a Pd/C catalyst (Scheme 4.125).436... 

Polymers such as polystyrene, poly(vinyl chloride), and poly(methyl methacrylate) show very poor crystallization tendencies. Loss of structural simplicity (compared to polyethylene) results in a marked decrease in the tendency toward crystallization. Fluorocarbon polymers such as poly(vinyl fluoride), poly(vinylidene fluoride), and polytetrafluoroethylene are exceptions. These polymers show considerable crystallinity since the small size of fluorine does not preclude packing into a crystal lattice. Crystallization is also aided by the high secondary attractive forces. High secondary attractive forces coupled with symmetry account for the presence of significant crystallinity in poly(vinylidene chloride). Symmetry alone without significant polarity, as in polyisobutylene, is insufficient for the development of crystallinity. (The effect of stereoregularity of polymer structure on crystallinity is postponed to Sec. 8-2a.)... 

Emulsion polymerization was first employed during World War II for producing synthetic rubbers from 1,3-butadiene and styrene. This was the start of the synthetic rubber industry in the United States. It was a dramatic development because the Japanese naval forces threatened access to the southeast Asian natural-rubber (NR) sources, which were necessary for the war effort. Synthetic mbber has advanced significantly from the first days of balloon tires, which had a useful life of 5000 mi to present-day tires, which are good for 40,000 mi or more. Emulsion polymerization is presently the predominant process for the commercial polymerizations of vinyl acetate, chloroprene, various acrylate copolymerizations, and copolymerizations of butadiene with styrene and acrylonitrile. It is also used for methacrylates, vinyl chloride, acrylamide, and some fluorinated ethylenes. 

The data on the reactivities of trichloroethylene and tetrachloroethylene further illustrate the competitive effects of substitutions on the 1- and 2-positions of ethylene. Trichloroethylene is more reactive than either of the 1,2-dichloroethylenes but less reactive than vinylidene chloride. Tetrachloroethylene is less reactive than trichloroethylene—analogous to the difference in reactivities between vinyl chloride and 1,2-dichloroethylene. The case of polyfluor-oethylenes is an exception to the generally observed large decrease in reactivity with polysubstitution. Tetrafluoroethylene and chlorotrifluoroethylene show enhanced reactivity due apparently to the small size of the fluorine atoms. 

With the great commercial interest in chlorofluorocarbons, the addition of HF to unsaturated organic chlorides, particularly vinylic chlorides has received considerable industrial attention.4 3 13-19 While these reactions are more difficult to effect than those of simple alkenes and increasing halogen substitution about the C—C double bond decreases the alkene reactivity, the reactions of simple monochloroalkenes proceed at temperatures from -23 to +120 C and can give good yields. Trichloroethylene or 1,1,2-tri-chloropropene, on the other hand, require temperatures in excess of 200 C, and tetrahaloethylenes fail to react in the absence of a catalyst.3 However, substitution of fluorine for chlorine tends to facilitate HF addition.3... 

ABA ABS ABS-PC ABS-PVC ACM ACS AES AMMA AN APET APP ASA BR BS CA CAB CAP CN CP CPE CPET CPP CPVC CR CTA DAM DAP DMT ECTFE EEA EMA EMAA EMAC EMPP EnBA EP EPM ESI EVA(C) EVOH FEP HDI HDPE HIPS HMDI IPI LDPE LLDPE MBS Acrylonitrile-butadiene-acrylate Acrylonitrile-butadiene-styrene copolymer Acrylonitrile-butadiene-styrene-polycarbonate alloy Acrylonitrile-butadiene-styrene-poly(vinyl chloride) alloy Acrylic acid ester rubber Acrylonitrile-chlorinated pe-styrene Acrylonitrile-ethylene-propylene-styrene Acrylonitrile-methyl methacrylate Acrylonitrile Amorphous polyethylene terephthalate Atactic polypropylene Acrylic-styrene-acrylonitrile Butadiene rubber Butadiene styrene rubber Cellulose acetate Cellulose acetate-butyrate Cellulose acetate-propionate Cellulose nitrate Cellulose propionate Chlorinated polyethylene Crystalline polyethylene terephthalate Cast polypropylene Chlorinated polyvinyl chloride Chloroprene rubber Cellulose triacetate Diallyl maleate Diallyl phthalate Terephthalic acid, dimethyl ester Ethylene-chlorotrifluoroethylene copolymer Ethylene-ethyl acrylate Ethylene-methyl acrylate Ethylene methacrylic acid Ethylene-methyl acrylate copolymer Elastomer modified polypropylene Ethylene normal butyl acrylate Epoxy resin, also ethylene-propylene Ethylene-propylene rubber Ethylene-styrene copolymers Polyethylene-vinyl acetate Polyethylene-vinyl alcohol copolymers Fluorinated ethylene-propylene copolymers Hexamethylene diisocyanate High-density polyethylene High-impact polystyrene Diisocyanato dicyclohexylmethane Isophorone diisocyanate Low-density polyethylene Linear low-density polyethylene Methacrylate-butadiene-styrene... 

The formation of coagulum is observed in all types of emulsion polymers (i) synthetic rubber latexes such as butadiene-styrene, acrylonitrile-butadiene, and butadiene-styrene-vinyl pyridine copolymers as well as polybutadiene, polychloroprene, and polyisoprene (ii) coatings latexes such as styrene-butadiene, acrylate ester, vinyl acetate, vinyl chloride, and ethylene copolymers (iii) plastisol resins such as polyvinyl chloride (iv) specialty latexes such as polyethylene, polytetrafluoroethylene, and other fluorinated polymers (v) inverse latexes of polyacrylamide and other water-soluble polymers prepared by inverse emulsion polymerization. There are no major latex classes produced by emulsion polymerization that are completely free of coagulum formation during or after polymerization. 

Other methods are described in Reference 61, however, the commercial process for the synthesis of vinyl fluoride is not described in the literature for proprietary reasons.61 Addition of HF to acetylene and fluorination of vinyl chloride are the most likely industrial routes to the production of VF.62... 

Chlorine-containing Polymers. Polymers containing one chlorine atom in various environments (other sustituents) were studied by XPS poly(vinyl chloride) PVC, poly(chlorotrifluoro-ethylene) PCTFE, an (ethylene-chlorotrifluoroethylene) copolymer, and poly(epichlorohydrine) PEPI, were chosen because besides carbon atoms they contain chlorine in presence of hydrogen, fluorine, and oxygen atoms. The valence band spectra of these compounds (see Figure 9) show that features can be easily and unambiguously assigned to a contribution from the chlorine molecular orbitals. 

An oxidizer. The liquid is a sensitive explosive. Explosive reaction with carbon disulfide (when ignited), methanol (when ignited), pentacarbonyl iron (at 50°C), phosphine + oxygen, sodium diphenylketyl, dichlorine oxide, fluorine, nitrogen trichloride, ozone, perchloryl fluoride (at 100-300°C), vinyl chloride. Reacts to form explosive products with dienes (e.g., 1,3-butadiene, cyclopentadiene, propadiene). 

Vinyl fluoride undergoes halogen exchange with B2CI4 to form vinyl chloride and fluorochloroboron derivatives [84). Simultaneously, but more slowly, the vinyl chloride is consumed by the reaction previously described to form l,l,2-tris(dichloroboryl)ethane. The fluorine originally present in... 

Some of the halogenated polyolefins are vinyl derivatives such as poly(vinyl chloride) and poly(vinyl fluoride), some are vinylidene derivatives, and others are polymers with even higher levels of halogenation. For example, from monomers of fluorinated ethylenes, the following polymers can be obtained ... 

The polymerization of unsaturated halohydrocarbons has been studied most extensively in the case of vinyl chloride and closely related compounds. Kainer 1S6) published a book recently on polyvinyl chloride and mixed polymers of vinyl chloride. In addition to chlorovinyl polymers, Schildknecht includes fluorovinyl polymers in his book Hl). Books covering plastics generally include material on the halohydrocarbon polymers (14, 144)- Several papers ISS, IS, 135,143) have been published in the last couple of years dealing with the polymerization of fluorine-containing compounds. Articles on polymerization of chloroprene 14 ), fluoroprene 1S8), chlorotrifluoroethylene 140), tetrafluoroethylene 1S9), vinylidene fluoride (157), and dichlorodifluoroethylene 1S7) have appeared in recent years. 

Figure 13 shows the excellent solubility of a vinyl chloride specialty copolymer in ketones. The fluorinated vinyl chloride copolymer also shows the same excellent solubility in ketones as shown in Figures 14 and 15. 

---